Chemistry 2nd Paper u Medical & Dental Admission CareOrganic Chemistry 221 Worked Example-2. (a) Write the structures of probable isomers of C3HsO (b) Write the structures of probable isomers of C3H¢O Strategy : Given formula C3HgO follows general formula C,Hyq120, which stands for alcohol and ether. Again C3H,0 follows CyH,0 which stands for aldehyde-ketone and alkenol. 'o determine isomers of aleohol-ether and aldehyde-ketone : Solution : (a) C3HgO has the following alcohol and ether isomers : Ho tebe pees ~ ee Hw f H bait x ood propanol} propanol-2 methoxy ethane (b) CsH,O has the following aldehyde, ketone and alkenol isomers : eteha |. MORAL] nitions ie ik i propanal propanone 2-propen-I-ol Students’ Work-2.9: Functional group based isomers of Ternary compounds Problem-2.17 : Write the structures of isorners of the followings : (a) Isomers of CHO having saturated carbon chains. (b) Isomers of CsHoO having keto-group. (©) Isomers of C4Hjo0 having all probable structures. (Isomers of CsHio02 having a—~COOH group. 2.8 Aromatic Hydrocarbons ‘The word ‘aromatic! was derived from the Greek word ‘aroma’ meaning sweet smell. In early days of orgnic chemistry, some compounds with sweet odour were discovered, which were found to possess properties different from aliphatic ones. These compounds were termed aromatic compounds. Later chemists found that, aromatic compounds differ from other organic compounds in chemical properties. Molecular structures of aromatic hydrocarbons are planar and cyclic but differ from cycloalkanes. Aromatic hydrocarbons contain rings of six C-atoms with alternate single bond (C-C) and double bond (C = C), (Benzenelisiconsideredtasithe primelcompoundlor ‘thistelass. Definition of Aromatic Compound : Benzene, benzene derivatives and benzene like unsaturated cyclic organic compounds which contain 'Huckel rule’ based (4n + 2) resonating pi222 Chemistry -2nd Paper (x) electrons, are called aromatic compounds. Here ‘n’ is number of ring in the compound; example. ‘He H ‘* 9 6 OT & GD Arenes They havevoneliorimorensix? (membered benzenoidiritig? For example, benzene, benzene derivatives, polynuclear naphthalene anthracene etc. Benzene Homologues : When one or more hydrogen atoms of benzene are replaced by alkyl groups, then the alkylated benzene derivatives are called homologues of benzene. Examples are toluene, ethyl benzene and xylenes. Disubstituted Benzene : When two hydrogen atoms of the benzene ring are substituted by two monovalent atoms or radical (same or different) the compound formed is a disubstituted benzene derivative. The second substituent can occupy any of the five rest positions of mono substituted compound. Numbering begins from position of first substituent by 1 clockwise. WWill Fespectto:first;group; Here'ortho'"(o)meansinearery So the second substituent goes to any one of three positions ortho, meta or para symbolically o-, m- and p-positions. Hence disubstituted benzene derivative has three isomers namely ortho-compound, meta-compound and para compound as follows : 3, S Co os 9 = ke i Sources of Aromatic compounds : (GslliquideeouI=Atae This coal-tar contains three types of aromatic compounds like acidic, basic and neutral, Again on fractional distillation of coal-tar upto 400°C, the following distillates are obtained.Organic Chemistry 223 Table-2.9 : Different Distillates of Coal Tar. Temp. range | % age by vol. Main compounds Light oil : 170°C (upto) % benzene, toluene, xylene, phenol, sp. gr. 0.97 pyridine, thiophene ete. . Middle oil : 171°-230°C 7.5% | phenol, cresols, naphthalene. sp. gr. 1.005 Heavy oil or Creosote: | 231°-270°C 10% | cresols, naphthalene, quinoline. sp. gr. 1.03 Anthracene or green | 271°-400°C 20% | Anthracene, phenanthrene oil = sp. gr. 1.09 Pitch residue left 57.5% __| Mainly coke carbons. 2.8.1 Separation of Benzene & Toluene from Light Oil Wightvoilycontains mainly) neutral benzene, toluene, xylene etc. hydrocarbons,{(6)Jbasic compounds aniline, pyridine, thiophene andi(@Jacidic compound phenols. Light oil is treated with conc. HySO, first and then with 10% NaOH solution to wash out respectively basic and acidic compounds (a) Removal of basic compounds : 2p + FSO, (aq) =e) 80% (aq) aniline anilinium sulphate: (b) Removal of acidic compounds : Oo + NaOH (aq) —> Orm (aq) + H:0@) phenol sodium phenate Then that light oil is washed out with water to remove residual NaOH once again. Later this light oil is seein distilled — and distillate is collected; it is called 0%6benzob fractionally distilled a ate this ebenze Purification : The 99% pure benzene separated from light oil, contains impurities like toluene and thiophene. OMPUFACHtIOn hisubenZeneNsIcoOled Natio CHMithMneeZingmmixturey (DHERNGERZEHEMOAEISEEYSALS which still contains impurity thiophene (0.5%). latenithatibenzeneiis? ay ay benzene: payer js ae a=224 Organic Chemistry | *Freezing Mixture : (1) NaCl and ice water (1 : 3) = ~ 22°C; (2) CaC.2H,O and ice water =~55°C; (3) acetone and dry ice (CO2) =~ 78°C, (4) ether and dry ice (CO;)=—100°C. 2.8.2 Preparation of Benzene and Toluene (A) Benzene Preparation: 1. Benzene from Sodium benzoate and Sodalime : ‘Whentaiimixture of sodium benzoate’ salt/and’ sodalimie!is’ heated;)benzene-vapour'(b p= '8014°C)\is|produced! On cooling that vapour, liquid benzene is obtained, MHisireaction between sodium salt of carboxylic acid and soda lime to form hydrocarbon with elimination of CO2, i81 (alledidecarboxylation: © + NaxCO; (CaO) Op-o00ne benzene Sodium benzoate 2, Benzene from Phenol : (Benzenevapour On cooling benzene-vapour, liquid benzene is obtained. (Coons za Ay © + Zn0 Phenol benzene m Ethyne or Acetylene : 3H-cecu Fe 450e 4. Benzene from Grignard Reagent : CeHe Onies\in’ contact with water it hydrolyses CoHsMgCl + HOH —> C¢Hg + Mg(OH)CIOrganic Chemistry 2s Owe +H3P0) + H,0-Cu4 “3 Cp + H3PO3 +N2+HCl B) Toluene Preparation : 1. Toluene from chlorobenzene ; \WHEHNANiMixtire tof chlorobenzeneyimethyliichloridetand’ ‘sodiuniiniétal dissolved in'dry etter is heated;:then toluenciis produced. This Feaction’is\knownias’ Ou +2Na +CHCl cutie Os +2NaCl chlorobenzene toluene Similarly, Teaction from aryl halide (ArX), alkyl halide (RX) and soldium metal dissolved in dry ether, on heating together. ar {XINaX] -R AMS aR + aNax 2. Toluene from Benzene :[injpresenés of dry/AICl; benzene reacts with methylichloride toy ‘(Produceitoluene/and HCI. (This réaction/is Galléd Friedel Crate alkeylation. © +cH,cl SY AIC Om +HCI benzene toluene 2.8.3 Molecular Orbital Structure of Benzene __-pMAT122-23 ‘Sixcarbontatomistim'benzene?areysp? Ot" Stew ‘Bybridised: Out of three, two hybrid orbitals of each carbon atorn q q form two o-bonds by overlapping with two hybrid orbitals of two F adjacent carbon atoms forming a planar hexagon (Fig-2.15). Then Oy, —O the third hybrid orbital of each carbon atom forms a sigma bond with : H atom by sp?-s orbitals overlapping. Each carbon atom still contains one unhybridised 2p) orbital perpendicular to planar ‘Fis. 2.15: planarhexagon with o-bonds hexagon. Then six 2p) orbitals of six carbon atoms overlap sidewise to form symmetrical molecular n-orbital. [Fig-2.16(a, b)]. The cloud of six n-orbitals remains delocalised above and below the plane of hexagon, h is shown in’Fig. 2.16(b). As a result — (A) carbon-carbon double bond (C=C) length in zene is 0.139 nm (or, 1.39 A) which is in between the value of single (C-C) bond 0.154 nm Chemistry-2nd-15(A)* 226 Organic Chemistry or, 1.54 A) and double (C=C) bond 0.134 nm. (or, 1.34 A) (B) So benzene does not give all lectrophilic addition reactions like () Bromine solution (Bry/CCI,) test, (ji) Bayer test (KMnOVKOH), (iif) addition of water in acid medium sttuilar to ethene or ethyne; but gives substitution reactions also. Fig-2.16(a) : planar hexagon in the middle. Fig-2.16(b) : delocalised x electron cloud over and overlapping p-orbitals above and below. above the planar hexagon. Kekule (1865) suggested that the carbon-carbon single bonds and double bonds are constantly changing their positions and benzene structure is a resonance hybrid. Resonance : Resonance in a molecule is the process by which two or more conventional valence bond structures with equivalent energy are formed by delocalised x electrons of the atoms already bonded with sigma bonds resulting a more stable hybrid structure. The reasonance hybrid structure of benzene is shown as follows : J resonating ep CO « Cy 2.8.4. Reactions of Aromatic Hydrocarbons ‘The chemical reactivity of aromatic hydrocarbons like benzene depends on its structure. From structural analysis of benzene by modern scientists with X-ray diffraction; it is found that : (1) benzene molecule is flat) hexagonal symmetrical with sp? hybridised six C-atoms, (2) carbon- carbon bond length in benzene is 1.39A which is in between the values of single bond (C-C) length (1.54) and double bond (C=C) length (1.34A), (3) Kekule (1865) suggested that the carbon-carbon single bonds and double bonds in benzene are constantly changing their positions in hexagonal structure and benzene structure is a resonance hybrid of six resonating x electrons. The resonance hybrid structures of benzene is shown as O-O « On eae In ethane, C-C bond length = 0.154 nm In ethene, C=C bond length = 0.134 nm Chemistry-2nd-15(B)Organic Chemistry 227 Unsaturation of Benzene differs from Ethene or Ethyne : By an analysis of different chemical reactions of benzene, it is found that : (1) Benzene (CgH,) is an unsaturated hydrocarbon but its unsaturation differs from that of alkene and alkyne. Benzene undergoes addition reactions with Hz, Clz, Brz vapour and O3, but it does not react with HX, HOX and does not give unsaturation test with Br2 in Clq solution and alkaline KMnO, solution. So benzene has a very special type of unsaturation. (2) Benzene is usually stable as it is not attacked by ordinary oxidising agent like cold alkaline KMnO,, but strong oxidising agent like acidic KxCr,07 on heating, breaks its structure. (3) Unlike unsaturated alkene or alkyne, benzene undergoes electrophilic substitution reactions like halogenation, nitration, sulphonation and Friedel-Craft’s reaction. During these subsitution reactions electrophiles attack the x-electron cloud, Practically delocalised n-electrons make the benzene more stable. So benzene gives both substitution and addition reactions. Hence the unsaturation in benzene differs from that in ethene or ethyne. Aromatic compounds like benzene undergoes mainly (i) addition reactions and (ii) substitution reactions both: (A) Electrophilic Addition in Benzene: * @) Addition with Hi : [inipresenice"ot catal ystiNi particles| heated at'200°O;\benzeneivapotty ‘and/H3jgasiadd up to form(cyclotiexanie: Each mole of berizenie!adds with three molesiof Hg. Itisia? (free-radical type'addition reaction? — 8 r 43% or ke HH cyclohexane ease @) Addition with Cl, : njpresence/onidireet/Suilightlorl UV rayslSiniolestofClyigasiadds \withyimolevof benzene |to! form! benzene hexa chloride lor gammiexane: It is also a free- radical type addition reaction. Rat £ H af ou oe Ka Me PE 3c, salt al la XH CH orwv we So of H benzene hexachloride CeHgCle benzene Bromine vapour adds with benzene to form benzene hexa bromide.228 Organic Chemistry ‘The above hydrogenation and halogenation reactions prove that as onelmiolelbenizeneladds) (3) Addition with ozone : A co, 82H HO 0 ng “pH 430, Se og ¢ 0, i + 3Z00 ms an He € slyoxal H 3 H tos benzene triozonide Know Moi ‘Simin -DUPRSEAAMBELOR AGHA) Because Bond !comiprisinig/ofart=bondand also 1 mole of triple bond comprising of two x bonds as in ethene and ethyne respectively. (B) Electrophilic Substitution in Benzene : @ Calalytic Halogenation : Definition : The reaction by which one or more H-atom of organic compound like benzene can be replaced by halogen atoms in presence of halogen carrier is known as halogenation. Halogen-carriers are Fe, P, Ip and Lewis acid like anhydrous AICls, FeCls, FeBry etc. Halogenation is an electrophilic. substitution reaction, Example. In absence of sunlight but in presence of halogen carrier like anhydrous AICI; (Lewis acid) the H-atom of benzene is substituted by chlorine atom to form chlorobenzene. Bromine also reacts in the same way but with a slower rate. hydrous, oO + Ch —aic, > + HCl benzene chloro benzene Reaction Mechanism : At first, from Cl, and AICI; form a nucleophile (AICI, ) and an electrophile chloronium ion (CI*) which, at 2nd step, is attracted by pi (m) electrons of benzeneOrganic Chemistry 229 ring to form sigma (a) complex. At last step, at the approach of the nucleophile one proton (H*) is eliminated from sigma complex to form chloro benzene. aca ssc; —» Alc + cr : nucleophile _electrophile oO AlCl, + HCl + AIC benzene electroptile complex chloro benzene ates) 'Q) Nitration : Definition : The reaction by which one or more. H-atom of organic compound like benzene can be replaced by corresponding number of nitro group (-NO>) is known as nitration. Nitration is carried out with conc. HNO; and cone. H,SO, af a high temp. [i127 Exampl \iitequalivolumesy one H-atom is replaced by nitro (NO;) group to forni nitro benzene and water. NO, conc.H,S0, + HONO, ye + HO * nitro benzene Reaction Mechanism : At first, stronger conc. H)SOz_acid supplies a proton (H*) to cone. HNO; acid to form water and electrophile nitronium ion (NO2) which, at 2nd step, is attracted by pix) clectron of benzene ring to form sigma (c) complex. At last step, at the aproach of the nucleophile like bisulhpate HSO, ion, one proton is given out from sigma complex to form stable product nitrobenzene. ae £ H,S0, + HO-NO, —> NO; + H,0 + HSO, clectrophile nucleophile + No, — Ofte. ig (Or oO 2 0, HSOp om. Hi80; benzene dlectophile g-complex nirobenzene (used again) @) Sulphonation : Definition : a temp. It is an electrophilic substitution. Example : At about 100°C temp. when benzene is heated with conc. H,SO, for an hour or with fuming HySO, i.e. HySO, mixed with SOs, at 40°C for 20 — 30 minutes benzene sulphonic acid and water vapour are produced, Here one H-atom of benzene is replaced by -SO;H group. \230 Organic Chemistry 03H oO +HO-SO;H 25 +H,0 benezene sulphonic. acid SO; + H,O—+H,S0, Water produced in this reaction is absorbed by SO, to form conc. H,SO, and creates favourable condition for forward reaction. Reaction Mechanism : At first, polar electrophile SO; is formed by dissociation of H,SO4 at high temp. Then electrophile SO; is attracted by pi () electron of benzene ring to form sigma (©) complex. At Jast step, at the approach of the nucleophile like bisulphate (HSO;) ion, one proton (H*) is given out from sigma complex to form benzene sulphonic acid anion which accepts a proton from reaction medium to form stable product benzene sulphonic acid. 1,80, + HO-SOM<= HOt + SO; + HSO, clectrophile nucleophile ode —_— obo, eB hs es & & Oo ois By oO”. 80. benzene S03 S03 + HjO" —> + H,0 (4) Friedel Craft’s Reaction : Definition : e rdrous Alkylation : + crc. | ees auiSl benzene toluene Mechanism of Alkylation : At first, electrophile methyl carbonium ion (*CHs) is formed from CHCl and AICIs, which, at 2nd step, is attracted by pi (1) electron of benzene ring to formOrganic Chemistry 231 sigma () complex. At last step, at the approach of nucleophile like, AICIé, one proton is given out from sigma complex to form stable product toluene. HjC@Cl F*AICI; ——> ECL t AID, oO * wo Gen By o™. HCl +AICl lb ve o-compkex toluene: H COCH; ‘. anhydroi Acylation : O + CHCocl “Sra > oO + HCl benzene a Mechanism ‘of Acylation : At first, electrophile acetyl carbonium ion (CH3C =O) is formed from CH;COCI and Lewis acid AICl3; which, at 2nd step, is attracted by pi (x) electron of benzene ring to form sigma (c) complex. At last step, at the approach of nucleophile like AICI, , one proton (H*) is given out from sigma complex to form stable product acetophenone. I - CEL FSAIC—> CHC + Alcs 9o > he w . COCHy O + ‘bow Chron es oO + HCL +AICl benzene o-complex acetophenone Know More :) benzene? [D.B. 2019] Solution : Friedel Craft's reaction and halogenation are electrophilic substitution reactions oceurred in aromatic hydrocarbons like benzene and toluence. In this reaction 'electrophile’ is the attacking reagent. So Lewis acid like dry or, anhydrous AICI3 is to use as catalyst to prepare ‘electrophile’ from main reagent by heterolysis of its covalent bond. Lewis acid, anhydrous AICI; molecule contains three bond pair electrons or, incomplete octet set. Hence anhydrous AICI can act as catalyst to form electrophile and nucleophile like AICI; from main reagents like alkyl chloride (CHC), acetyl chloride (CHyCOCI) and Clz molecule as follows :232 Organic Chemistry + ny (@CH3.Cl + AICI (dry) —> CH3 + AICI; (nucleophile) acne baci + AICh (dry) —> curd + AICI; (nucleophile) Gi)CIicl = # AIC (dry) —> crt + AICI; (nucleophile) Here as Lewis acid, dry AICls, dry FeCls or dry BF3 etc. are used. Lewis acid anhydrous AICI; is to use to prepare necessary electrophile. Otherwise, in presence of moisture or water AICls is hydrolysed to Al(OH)3 and HCI acid. AICI; + 3H,0 ==Al(OH)3 + 3HCI ‘ Then AICI; can not act as Lewis acid to prepare electrophile. 2.8.5 Aromaticity Chemist Eric Huckel, in 1931 extended the idea about aromaticity on the basis of delocalised ectrons in cyclic structures. His thought does not only limit aromatic properties to benzene and its derivative but also it includes cyclic ions and many heterocyclic compounds also with essential ondition of having delocalised x electrons to form molecular orbital. This concept is known .s Huckel theory. The necessary conditions proposed by Huckel for aromaticity in a closed chain sompound is called Huckel rules. Huckel rules are as follows : (1) The structure of organic compound must be flat or coplanar cyclic. The cyclic structure may be of five or six atoms. The bonding orbitals in the conjugated ring system must be completely filled. (2) Each and every atom forming the ring must contain p-orbital. The p-orbitals perpendicular to the plane of the ring being delocalised should overlap sidewise above and below the plane to form cyclic molecular orbital. This cyclic molecular orbital in organic compound must contain delocalised (4n + 2) n-electrons. Here 'n' indicates the number of five or six membered ring and n= 0, 1, 2, 3 etc: (i) When n=0, then total delocalised n-electrons = (4n + 2) = (4 x 0 + 2)= 2; it indicates cyclopropenyl cation. It contains a ring less than 5 members; so the value of n= 0 (ii) When n = 1, then total delocalised x-electrons = (4n + 2) = (4 x 1 +2) = 6; it indicates compounds of benzenoid ring or heterocyclic 5 or 6 member ring like furan, thiophene or pyridine etc. (ii) When n = 2, then it is naphthalene, when = 3, then it is anthracene ete. (3) In 5 membered heterocyclic compounds, lone pair p-orbital electrons of hetero atom (i. e. N, ©, S) takes part in delocalised n-electrons to fill up the rule of (4n + 2) x-electrons number. - The cyclic organic compound containing Huckel number delocalised n-clectrons in the ring ets more stability and gives special substitution reactions known as aromaticity. The structural formulae of such compounds are as follows :Organic Chemistry 233 ‘ 9 9 Y Woe cxeepropenyeton a ytidine net av}~ 6 f4ns2]=6 anv 3}= 6 Gn 0 antes Know More :] (1) The 5 membered pentagonal heterocylic furan, thiophene and pyrole each has two pi (n) bonds i.e 4 pi () electrons in the structure. But in these compounds lone pair electrons of the hetero atom N, O. S (in their p-orbital) take share with those 4 electrons to complete 6 electrons set as resonating electrons supporting "Huckel rule! (4n + 2). So. pyrole furan [> & thiophone [__>S each is an aromatic compound. (2) Naphthalene is an aromatic compound : explain [Ctg. B. 2017] laphthalene (CigH) has two condensed benzene rings containing 5 double bonds ie 10 jonating pi (7) electrons which follows Huckel rule (4n + 2). Here n = 2, hence total pi (7) Jectrons will be (4 x 2+ 2) = 10 and naphthalene molecule contains 10 resonating pi (z) Jectrons in its two ring-structure. So naphthalene is an aromatic hydrocarbon. 2.9 Differences between Aliphatic and Aromatic Compounds We have already known about open chain and closed chain organic compounds during their classification. Among the cyclic aliphatic and aromatic organic compounds structural differences Al aromatic hydrocarbons contain benzenoid ring which is(formedibyrsixispahybridiseay (moléctlarforbital! We have also known that {hybridised. In alkene, pi () bond electrons of carbon-carbon double bond (C=C) remain confined between the (twolG-atoms\withia/bond!lengthi O1S4iimi. But injbenzenoid ringsix!pi(@)iclectrons Femainyresonating,withralbond lengttil0ON39mi. For this benzene.structure attains more stability. More stability of the benzenoid ring containing six resonating pi () electrons creates cial characteristic differences in properties between aliphatic and aromatic compounds. 1¢ to more stability of benzenoid ring and having its bond length in between ‘bon-carbon single (C-C) bond and carbon-carbon double (C=C) bond, aromatic hydrocarbons jive substitution reaction like alkane (with Cl, and AICI3) and giveaddition reaction like alkene (with Cl, in UV ray). Those characteristic properties of aromatic compounds are called romaticity. We have already known Huckel theory to explain-aromaticity of hydrocarbons ntaining benzenoid ring and heterocyclic aromatic compounds. Huckel theory makes the clear ifferences in properties related to electronic distribution in structures of aliphatic and aromatic compounds.234 Organic Chemistry The main differences between aliphatic and aromatic compounds are given in tabular form % composition of carbon: 3. Saturation or unsaturation in C-chain : , 4. Test with Br, in CCl, and Bayer’s Test with alkaline KMn0,: 5, Reactivity of | Halides : 6. Nature hydroxy ‘compounds : of| 4, 6. }. Carbon single C-atom and lower percentage of carbon. In CHy, C= 75%, H= 25%. chain in aliphatic compound may be saturated or unsaturated. Example. CH3-CH; CHy-CH) ethane ethene, Aliphatic x-bonded unsaturated compounds add with red Br, soln, and pink KMnO, soln. with decolourisation. cc CHy=CHy+ Bry “4 cryBr.cH,Br 00H ra KMnO, OOH CHECH AIO" cee an . Aliphatic halide (R-X) is more reactive and easily hydrolysed in aqueous KOH soln. to form alcohol. CHCl + KOH(aq)->CH30H + KCI Aliphatic hydroxy ‘compound is called alcohol and litmus neutral. So it reacts with Na metal to form Hp gas. 2CH3OH + 2Na > 2CH3ONa + Hy Ww Points of Aliphatic compound Aromatic compound Differences LaSbractira 1. Aliphatic compounds are mainly|1. Aromatic compounds are open chain. Some closed chain] closed chain, planar and compounds with —similar| molecular structure gets properties are also present.) — stability with (4n + 2) Example, cyclohexane (CHt2) resonating x-electrons. 2, Number and| 2" Aliphatic hydrocarbon may be of| 2. Aromatic hydrocarbon must contain six C-atoms benzenoid ring and higher percentage of carbon. In CH; C= 92.3%, H =1.1% 3. Aromatic structural ring gets special stable unsaturation due to (4n + 2) resonating = electrons only. 4, Benzene adds with Hy indicating presence of 3 double bonds. Yet benzene cannot decolourise red Br) soln and pink colour of alkaline KMnO4 soln. These tests indicate - bonds in benzene ring stable and special. 5. Aromatic halide is less reactive and hardly hydrolysed at high temp. and high pressure to form phenol. } 6. Aromatic hydroxy compound is called phenol and tums blue litmus red as acid and reacts with NaOH to form phenate salt. 1 Na Goma } +H,0 1H KOH(q) +KCl 300°C, 200 atmOrganic Chemistry 235 cine of Aliphatic compound Aromatic compound ifferences 1. Addition, 7. Addition : In alkene, alkyne|7 Addition : Benzene adds with . _ i cs Hp and Cl, by free radical Substitution, electraphilic addition and in| jy 2chanism. Elimination: carbonyl (C=O) compounds} Substitution : Benzene ring é nucleophilic addition occur. contains mobile n-electrons Bes Artes 210] i and . hence — electrophilic Substitution: ‘Nucleophilic i bstituti il substitution occurs in R-X cicterene enbstinition; _ lke halogenation, nitration, compound. sulphonation, Friedel Craft Elimination : Alkene forms reaction etc. occur as the main from R-OH with H,0 reactions. elimination by dehydrating} Elimination; phenol (CsHsOH) agents and (ii) from R—X with and R-X give no elimination HX elimination by KOH (alc.) reaction. Students’ Work -2.10 : Home Work: : After reading this article, every student has to make a table of differences between aliphatic and aromatic compounds with the following points of differences and is to submit the note Khata to his class teacher to assess. Point of Differences : 1. Carbon chain, 2. Number of C-atoms, 3. Electrophilic addition, 4. Electrophilic substitution;, 5. Carbon-carbon bond length, 6. Structisral stability, 7. Huckel rule. ‘Worked Example- 2.7 : Benzene Related Chemistry : (Di. B. 2016] Solve the questions related to following stem : All ik [Rg] or te, BOLE camp (a) How does sp-hybridisation occur in compd. (A) of the stem ; explain? (b) Explain the mechanism of the reaction to prepare compd. (C) from compd. (B) as per stem, Solution : 2(a) As per given stem, Compound (A) is an alkyne containing two C-atoms ; hence it is acetylene or ethyne. In compound ethyne there is a triple bond between two C atoms (H-C=C-H). Here each of the two C-atoms with excited state mixes its 2s orbital with any one 2p orbital like 2p, orbital to form two new equivalent hybrid orbitals 2y}, 23. These two hybrid orbitals are coplanar and lie in a same straight line. *C (6) 1522s! 2pl 2p), ap), SPAVDridisation, 12 ay 2 y) 2p) app236 Organic Chemistry For the formation of ethyne molecule (C;Hz), at first two sp-hybridised C-atoms form carbon-carbon sigma bond by overlapping two hybrid orbitals of two C-atoms. Then remaining two hybrid orbitals of two C-atoms form two sigma (9) bonds with Is' orbitals of two H-atoms. Thus two C-H bonds and one C-C sigma (o) bond are formed and all the atoms lie on a plane. ng -bond ™ bond side-wise ‘bond Py Py & Pre Ae. Hoey Hn > a hopping Gh A cor acetylene A PoP Fig-2.18 : ts of ethyne molecule by one sigma and two pi(n) bonds between two sp hybridized C-atoms. Still each C-atom has two unhybridised 2p,' and 2p', orbitals perpendicular to each other. Then 2p, orbital of one carbon atom sidewise overlaps partially with 2p, orbital of other carbon atom to form a pi (n) bond. Similarly 2p, orbitals of two C-atoms overlap partially to form second pi (nt) bond. Thus one sigma (a) bod and two pi (7) bonds between two C atoms form a carbon-carbon triple bond of 0.120 nm length in acetylene molecule. Solution-2.(b)The given stem is as follows : io") we @) ac = ad (©) compound Preparation of (C) compound from (B) and its mechanism : ‘Two carbon atoms containing alkyne is acetylene. So ‘A’ compound is acetylene (HC=CH). Here when acetylene gas is passed through a iron pipe heated at 450°C, then benzene is formed by polymerization of three molecules of acetylene. 3 H-C=C-HFeA50°C, acetylene benzene (B) Now at 60°C, benzene is heated with cone. HNO; acid in presence of cone. H,SQ, to produce mononitro benzene or (C) compound. ‘NO: + HO-No, 1:S01(cone) Oo * + #0 benzene nitrobenzene Mechanism of Nitration : () First step : Formation of electrophile (NO;) : The stronger conc, H,SO, supplies a proton, then conc. HNO; accepts the proton to form water and nitronium ion ((NO;) as follows :Organic Chemistry 237 H,S0,+ HO-NO,—>NO, + H,O + HS0s electrophile nucleophile Gi Second step : Formation of sigma (o) complex : The electrophile nitronium ion (NO;) is attracted by the delocalised n-electrons of benzene ring and they join up together to form an unstable intermediate sigma (c) complex. ° HNO: O + %. — 6 o-complex Third step : Removal of proton : Sigma complex releases a proton at the approach of nucleophile HS; ion and forms stable product nitrobenzene MAT:99-2D "eS O @1C0:208 What is carbon- & + HSO; = + HySO, carbon bond length in benzene? o-complex ikcbell ne (130A (6) 134A © 139A @ 154A 2.10 Different Reactions of Aliphatic and Aromatic Compounds Now in this article, we shall know the different organic reactions of aliphatic and aromatic compounds such asgi/Paddition (electrophilic and nucleophilic), @P substitution (electrophilic and nucleophilic), @§P elimination, @ rearrangement or isomeric change, (5) multiple substitution in benzene ring and orientation. From a mechanistic view, it is believed that an organic reaction takes place by the attack of a reagent like Cl, or HBr on an organic compound knowa as a ‘substrate’ which means ‘lying below’. So in an organic reaction, three terms like (i) attacking reagent, (ii) Substrate and (iii) Produet are used : Attacking reagent + Substrate —» Product le = x + YZ — KY +Z tacking reagents are of 3 classes : free radical, (2) electrophile and (3) nucleophile. GeeeRawioale When covalent bond of a reagent is homolysed or breaks symmetrically, in presence of heat energy or sunlight (hv), free radicals with unpair electron are obtained. ce-cl hy, homolysis 396 KMimol Cl + °C! [bond dissociation energy of Cl, is 2433/mol]238 Organic Chemistry By homolysis of carbon-carbon sigma en of an alkane, alkyl free radicals are formed. HyC-«CH,CH, Heal, «cH, + *CH;CH; methyl ety! free fieeradical radical Reactivity and Stability of Alkyl Free Radicals : Free radicals, having unpaired electron, become very reactive. Stability of alkyl free radicals depends on the nature of their carbon atoms. 3 alkyl 2° alkyl Ialkyl methyl free radical free radical free radical free radical (1°) ** Note : More stable free radical gets more chance to react with reactant. Unstable groups generally get less time to react. Electrophile & Nucleophile : When covalent bond of a reagent breaks unequally or heterolyses under the influence of a solvent or a catalyst, then positively charged atom or radical called electrophile and negatively charged atom or radical called nucleophile are formed. For example; catalyst “Bogert A * BF nucleophile clectrophile Examples of nucleophiles: 5. pS CNC Ben © Examples of clectrophiles: H',-HO*, NO}, S0;, ANCL, FeCl (Carbonium ion Carbonitim|ion’is/an organic’ radical’ containing’a’carbon’atom withtunit \positivercharge. [tistalsovealled carbocation. It is denoted by R*. Examples are (i) methyl carbonium ion (& Hs), (ii) ethyl carbonium ion (CH3¢ Ha) Formation : In case of alkyl halide (R-X) like methyl chloride (CH3-Cl), Cl-atom is more clectronegative than C-atom. So Neterolyi6:HSSiGH GF breaking of covalentiboridvoccurs. So a positive charge developes on C-atom of CH group. Thus methyl carbonium ion (eu) is formed. chloride ion dtl eee, wl +- ocr i ih methyl chloride methyl carbonium ion Reactivity and Stability of Carbonium Yon : Carbonium ion contains six electrons in bond shell and has highest tendency to form octet set by reacting with electron pair donor. SoOrganic Chemistry 239 carbonium ions are electrophiles. With increase of number of -CHy group attached to positive C- atom of the carbonium ions, their stability increases. Their stability order is shown below : ay {charge \Itis generally denoted by'R:. Examples are (j)/methyl/"carban fon (sC'H3)y tliyl'earbar? iomGCH:CHRY Formation : (Acidic/o=Hcontainingycarbonyl compound like"ethanal'forms’carban iionviny Presence‘of dil: NaOH solution? OH- + H~ CH,CHO —> :CH,CHO + H,O [here a~His acidic ]. base ethanal carban ion [The C-atom joined with functional group is called alpha (a. carbon and H-atom attached with @-C atom is called o-H atom.] Reactivity and Stability of Carban Ions : Carban ions are very reactive and shortlived. They act as nucleophiles (positive end loving). Generally they take part in addition and substitution reactions. With the increase of number of -CHy group attached to negative C-atom of the carban ions their stability decreases. Their stability is opposite to carbonium ions and is shown below : as) ¢ ay 6) Electrophile or Electrophilic Reagent : Electrophiles are electron loving attacking reagents. They are short of a pair of electrons than stable electron set like duplet or octet. So they accept pair of electrons in a reaction. They are denoted by E. Electrophiles are of two types. Positive Electrophiles (E*) : They are positively charged ions or radjeals. Examples are ethyl carbonium ion (CHs), hydronium ion (H0*), nitronium ion (NO,), proton (H*), romonium ion (Br*) ete, DAT! 21-22 (2) Neutral Electrophiles (E) : [They are neutral molecules with short of an clectron-pair ible octet set. Examples are|AICsJ FeCl, BF3, SO3 etc. Attack of Electrophiles : Both types-of electrophiles can attack the electron-rich site of the substrate ion or molecule which can supply an electron-pair to the attacking reagent to form a new bond. i j (@ Attack by positive 4 bea m, electrophile : . (ii) Attack by neutral om" electrophile : - +25240 Organic Chemistry Nucleophile or Nucleophilic Reagent : Nucleophiles are nucleus-loving or positively charged centre loving reagents or substances. They have at least one pair of electrons which can be supplied to other reactant to form a new bond, They are denoted by Nu. They are of two types. ‘Negative Nucleophile (:Nu-) : They are negatively charged ions or radicals and their entral atoms bear a pair of electrons, Examples are methyl carban ion (:CH3), chloride ion CP), Bromide ion (:Br-), cyanide ion (:CN-), hydroxide ion (:OH>), alkoxide ion (:OR). (2) Neutral Nucleophile (:Nu) : They are neutral molecules bearing one or two lone pair of lectrons on the central atom. Examples are ammonia (NH3), water (H-O-H, alcohol (R--H) Attack of Nucleophiles : Both negatively charged and neutral nucleophiles have one or two electron pair. When they attack an electron deficient substrate, the Jater accept the spare electron pair from the reagent to form a new bond. om fe @ Attack of negative an +t nucleophile : No (il) Attack of neutral nucleophile : nn —tini of + Mi 2.10.1 Addition Reaction The reaction in which a new organic compound is formed by the combination of two different molecules is called an addition reaction, Additionsreactionfoccurstinvcompounds\containingi==) (bond. OS (Eoxygenldouble\bond in{earbonyl/groupl(OC=0)yeomipouiids? In addition reaction x-bond breaks down to form two new o-bonds with reactant molecules. * The x-electron-density in carbon-carbon double bond (C=C) and triple bond (C=C) remain equally distributed between two C-atoms. * But in carbonyl group (y¢=0) carbon-oxygen double bond, melectron gets attracted to oxygen atom more and polarity developes. i (Derizene|separatelyformingvetliane(andreyelohexané: Here catalytic hydrogenation occurs in free radical mechanism by dissociation of Hy molecule into two H atoms.Organic Chemistry 241 1 fig pom + me eS ii < a so 2S ef ethene Pog OH ( Electrop! Addition with Alkene & Allyn . Here carbon-carbon double bond (C=C) and carbon-carbon triple bond (C=C) w-electrons are moveable and act as electron donor towards electrophile reactants, The reactants like Cl, Bro, HCl, HOBr, HzSO4, HO, Oj etc. in solution or by the influence of n-electron, dissociate into positive electrophile and negative nucleophile as follows : ci:cl —> cr +:¢cr HO:Cl =—+CI* +:0H- Br:Br —> Brt +:Br- H :OSO;3H —+Ht +:0S03;H H:Cl —> Ht +:cr H:OH —+Ht +:0H- HO:Br —>» Brt +;OH- E:Nu —> Et +:Na (1) Addition of Halogen (Ch, Br) in Alkene and Alkyne Anmabsenicexof light-Cls-and Bry inrsoivent carbon tetrachloride (CCl4) add with x bond of” alkene:andvalkyne to prodiceldibalo and tetahalo’saturated'compounds. Example, CH;CH= CH, +Cl, Ck, CH CHCI-CH,CI propene 1, 2-dichloro propane CHC=CH + Br, C4, cH,CBr= CHBr 38 CH,CBr2—-CHBr) wropyne agiai2stemabrompropane Mechanism of Addition of Br, or Cl, in pi (x) bond (At first, by the influence of n-electrons dipole forms in bromine molecule (Bt- Br) . Gi) Secondly, Br part of dipole gets bonded with r-clectrons to form a sigma bond 4 Br part gets separated as bromide ion (Br). (iii) Finally unstable carbocation is formed and this carbocation adds with nucleophile bromide ion (Br~) rapidly. Chemistry-2nd-16(A)242 Organic Chemistry "in JB abe fe charge transfer (nucleophile) complex, carbocation 1, wien ethane Bromine colour Test for detection of x bond depends on this addition reaction. (2) Addition of Unsymmetrical Reactant with Unsymmetrical Alkene : When same number of H atoms remain bonded with both the C-atoms of the double bond, then that alkene isieallediSymnnTecEAANEHE? Example, ethene (@HSE=SI0H5) is an symmetrical alkene, (alkenes are called unsymmetrical alkenes} Forexample)) ‘ropene!(CHs=CH=CH1) sian unsymmetrical alkenes MaT10.2- 22 (@ Alkene's Reaction with HCI and HBr : Addition reaction of symmetrical alkene with unsymmetrical reactants like HCI, HBr, only one product is formed. Example: CH=CH + HCl—> CH; -CH,Cl CH3CH=CHCH; + HBr—»'CH3CH, - CHBrCH; (unsymmetrical ireactants|like/HCl; HBr HOCI; H3S0;'cte? Which of the additive two products will be primary product or, more in percent is known from Markovnikov’s rule established in 1869 by Russian chemist, Markovnikov. (MFKOVEIKGWSRULET When an unsymmetrical alkene undergoes addition reaction with an unsymmetrical reagent (like HBr or HOBr), the negative part of the reagent gets added to that carbon atom of the double bond containing less number of H-atom. Alternately : Markovnikov's rule may be stated as, the positive part of a polar additive reagent gets added to that x-bonded carbon atom which has more H-atoms. Example : When HBr reacts with propene, two types of products are possible; one is 2-bromo propane and the other is 1-bromopropane. Practically observed that 90% 2- bromopropant er with 10% 1-bromopropane are produced. CH;-CHBr-CHg , 2-bromopropane (90%) reir bet “H+ 2a (CHy—CHy-CHgBr , 1-bromopropane (10%) Chemistry-2nd—16(B)Organic Chemistry 243 Explanation : At first, from the unsymmetrical reagent HBr, electrophile H* ion and nucleophile bromide ion (Br-) are formed. Then electrophile H* ion is attracted by n electrons of double bond to form more stable 2° carbocation in more numbers, together with less stable 1°carbocation in Jess number. At last step, bromide ions get added with carbocations to form additive products. —CH,-¢H-cH, 2, CH;-CHBr-CH (90%) 2CHy-CH=CHy + aitez —| 2° carbocation (more stable) propene \_+CHs-CH,-CH, _Bi 2, CH;-CHy-CH,Br (10%) 1° carbocation (less stable) Anti-Markovnikov's Rule: Scientist Kharasch observed in 1933 that\ifipRESeHCelOP Organi@ (MarkovnikoVs1il@ That is, the negative part of the reagent gets added to that double bonded C-atom which has more H-atoms in presence of organic peroxide. [his\is|knownla’ Example : In presence of alkyl peroxide HBr adds up with propene to produce 99.1% 1- bromo-propane and 0.9% 2-bromopropane, : RO-OR .- PC CHa CH Br (99.1%) 2CH;~CH=CH, + 2HBr—4 propene -O-O-R. cH,-CHBr-CHs (0.9%) Explanation : Organo peroxide dissociates to form two alkoxy (RO.) free radicals. This free radical attacks HBr to produce bromine free radical (Br.) which attacks propene to form more stable 2°-bromo alkyl free radical. This 2°-bromo alkyl free radical attacks another HBr to form 1-bromo propane. ; Ist step : R-0:-0-R — —* RO. [organic free radical] RO. + H+ Br —> ROH + Br. [bromine free radical] 2nd step : a + BOR —~ BrCH,—CH-CH, ‘2°-free- radical (more stable) carb —- cH,—cHBrtH, 1°-free-radical less stable) 3rd step: More stable 2°-free radical reacts with second HBr forming anti-Markovnikov's product I-bromo propane 99.1% and a new bromine free radical (Br.) which propagates the chain reaction. iOrganic Chemistry Fee * BrCH,—CH-CH, + H++Br ——» BrCHy-CH)-CH,+Br 1-bromopropane. Note : 1) In Markovnikoy's rule : Addition reaction follows ionic electrophilic mechanism. (2) In Kharasch rule : Addition. reaction follows free radical mechanism initiated by organic peroxide free radical. 3) Kharasch rule is followed by HBr addition only; not with HCI or HI. _ Gi) Alkene's Reaction with H,SO, : According to Markovnikov's rule alkene reacts with conc. HySO, to form, firstly alkyl hydrogen sulphate by electrophilic addition. Then the product, on hydrolysis, produces alcohol. CH=CH + H-OSO3H—> CHy-CH,-080,H #29 cH,cih-oH + 1,80, ethene ethanol SoH 1H *H,CH=CH, + H-OSOsH—> CH; —CH—CH > Si de + H,SO, propanol-2 iii) Alkene’s Reaction with Ozone : Addition reaction of ozone with alkene is a complex ‘lectrophilic reaction. But ozone addition reaction is important for determination of position of louble bond in alkene chain. When ozone gas is passed through alkene dissolved in inert solvent like carbon tetrachloride (CCl), ozone reacts with double bond to form ozonide additive mpound. The ozonide, on warming with water and Zn powder is hydrolysed to aldehyde or ‘etone or a mixture of both and HQ. or nascent oxygen atom [0] depending on double bond sition and alkene structure. On adding Zn dust HyO2 is converted to ZnO. Otherwise H2O2 or ascent oxygen [O] may oxidise aldehyde to carboxylic acid. ‘4 5 2 4 Os. O PB CHC CHC, > CHs.CH— 6 CCl Ha Bes CH;CH,CHO + HCHO + ZnO mined 4 a Ppropanal ‘methanal ozonide (1 mole) (1 mole) dar dueeas é Os. . H,0,4 & CHCH=CHCH; Gop Crd CitcH “Z> 2CHs—CHO +Zn0 ‘butene-2 +. ethanal (2 mole) ozonideOrganic Chemistry 245 Ib wt oe ie oe eet CHy Ke Bg 9 CH LQ CH; + H- 7 H+ZnO 2-methyl propene aane propanone —methanal (mole) (I mole) Note : Here butene-1, butene-2 and 2-mehtyl propene are 3 isomers of CyHy molecular formula, Conclution : On hydrolysis of ozonide, if methanal and propanal mixture is obtained, then jat alkene will be butene-1; but when only ethanal is obtained, then that alkene will be butene-2. haf pe i H,0,4 : CH, e H Hy 3p CH,CHO + CH,COCH, + ZnO 2-Methyl butene-2 ethanal —_propanone By Hs et, ce = a4 2CH,COCH, + ZnO ., 3-Dimethy] butene-2 (propanone ozonide ‘Again on hydrolysis of ozonide, if ethanal and propanone mixture is obtained, then that alkene will be 2-methyl butene-2; but when only propanone is obtained, then the alkene will be 2,3-Dimethy! butene-2. Thus ‘determined by ozonolysis) Ozonolysis : CH,CHO + [0] —> CH;-COOH; CHy-CO4CH, + 4 [0] —»CH;-COOH + CO, + #20 Ozonolysis is used to determine the position of x bond in carbon chain. 3) Addition ‘of Unsymmetrical Reactant ‘Alkyne (i) Addition of HCI and HBr with Alkyne : With two n-bonds of alkyne addition goes in two steps. Here Markovnikov's rule is collowed : RC=C-H+Hx—4, R-CK=CH,—HX, R-CX,CH3246 Organic Chemistry ‘ HCeCH + HCIg) aC cu-cuct #O@ cy,cuci, vinyl oie ctviekene crite i Addition of water (H,O) with Alleyne :linpresencelof 2% mercuric sulplate/and! 207% ail FgSO,rat "60°C 75°C, alkyie adds with Water to" formaldehyde" oriketan. Here enol is formed by joining of H and OH group at two C-atoms with o-bonds after breaking of a pi (x) bond. Lat 1H 2% Hg? X en HC=C-H + HOH ZEEE, +0 SE ethyne 20%H2S04 vinyl alcohol (enol) ethanal 2+ H CHy-CaC-H+H-on 22H rearrangg & i- 20%ELS6, H > ~—CH;-C-CH; Propyne 2-propenol ‘Propanone (ii) Addition of Ozone with Alkyne : Triple bond position determination : When ozone gas is passed through alkyne dissolved in inert solvent carbon tetra chloride (CCl,) first ozonide is formed. Then ozonide gets hydrolysed on warming with water to form a diketone and HzO. Then diketone is oxidised to carboxylic acid by H,Q2 produced. (@) CH,CH,-C=C-H + 0-54, oni pe ag ci-cn£ ky +O, ‘butyne-1 2-oxobutanal: ozonide cnpcr-hilensmen -A, ca on-oH Ge on ‘2-oxobutanal Propanoic acid formic acid - CCly, YX eg = + ) CHy-CaC-CH; +0; 4, gy, cy 22 g g cad sie, butyne-2 A 2, 3-butandione cnt cu, +H,0, —4> norton 75nd _sthanoie acid (2- motecules) ‘(Conelusiongs After hydrolysis of ozonide formic acid and propanoic acid will be two products, when parent compound is butyne-1. But after hydrolysis of ozonide only ethanoic acid will be the product, when parent compound is butyne-2.Organic Chemistry 247 ‘@) Nucleophilic Addition Reaction of Carbonyl Compounds ‘Nucleophilic addition reaction occurs with divalent carbonyl group (_)0=0) of aldehyde and ketone. Here pi (x)-electrons of C=O group is more attracted towards O atom due to great difference of electronegativity in 0 atom and C-atom (3.5 —2.5 = 1.0). As a result partial negative charge is developed on O atom and partial positive charge on C-atom (Sf-43°). Then partial positive charged C atom of polarised carbonyl group is attacked by nucleophilic reagent easily and nucleophilic addition occurs. Here attacking nucleophiles are cyanide group CN of HCN, sodium sulphite group :0-SO,Na of NaHSO3, ammonia NH3 and Grignard reagent RMgX. () Addition of H-CN with Carbonyl Compound : All aldehydes and most of the ketones add with hydrogen cyanide (H-CN) to form cyanohydrins as nucleophilic products. os O + HCN ton, =0 + on —into aldehyde ketone aldehyde a adhe ketone cyanohydrin Mechanism of Nucleophilic addition : In dil. NaOH solution, HCN ii ionises more. Then more : CN ions produced, attack partially positive charged C atom of group. At last step, negatively charged O-atom accepts one proton (H*) from water (HO) molecule and thus addition ends. H-CN+:0-H—+H,0 + :CN Similarly carbonyl compounds react with NaHSO3, NH3 and methyl magnesium bromide (CH3MgBr) called Grignard reagent to give nucleophilic addition products as follows : (i) Reaction with sodium bisulphite and carbonyl compounds : ‘a Gis Hh CH. —be SPH-NSON— CHy—-b-o—g CH; G= +B. 9S0Ne—> CH C—0-H oul bso.va a OSO;Na cthanal propanone: sodinn tape sodlua bisulpite The bisulphite additive products of aldehyde and ketone are crystalline solids. So this reaction is used to separate aldehyde and ketone from other organic compounds.248 Organic Chemistry Gi) Addition with ammonia (NH) : Except formalin (40% methanal solution) other aldehydes and ketone like ethanal and propanone react with ammonia separately to produce crystalline additive product like ethanal ammonia compound and propanone ammonia compound. epi Fa ethanal ammonia Note : Formalin, a 40% aqueous solution of formaldehyde (H-CHO) gas, does not give yucleophilic addition reaction, but gives a condensation reaction between six moles of H-CHO d four moles of NH; solution, on heating, producing hexamethylene tetramine or hexamine, a edicinal product used in rheumatic fever and urinary tract infection. Hexamine from formaldehyde : When formalin is heated with oncentrated ammonia, a white cyclic organic compound’ hexamine or tropine is formed. Hexamine is ammonia formaldehyde cyclic polymer. Its | a chemical name is hexamethylene tetramine. Ha it 2 6H-CHO + 4NH; 4+ 6H,0 + (CH2) 2°R-X > 1° R-X te bimolecular ‘nucleophilic substitution substitution depends on the molar concentration of both alkyl halide and the nucleophile, then it reaction is called bimolecular nucleophilic substitution or Sw2 reaction. Definition of Sy2 reaction : When the rate of reaction of the nucleophilic haracteristics : (i) 1°-alkyl halide favours $y2 reaction because here steric hindrance towards tacking nucleophile is less, (ji) Sy2 reaction occurs in one step, (iii) here nucleophile attacks the